The mamekogane and the cupreous chafer are vermin on fruit trees such as grape trees, and lawns. In recent years, damage to lawn by the mamekogane and the cupreous chafers in golf courses poses a serious problem.
Conventionally, these mamekogane and cupreous chafers are exterminated by pesticide applications. However, since a large amount of pesticide is used, the environmental pollution caused by contamination with pesticides in the vicinity of a golf course is a serious problem.
On the other hand, catching and killing by attraction using the sex pheromone of a vermin has an advantage in that a large number of vermin can be exterminated with a small amount of pheromone. This method is applied to some vermin in practice. Therefore, catching and killing by attraction of the mamekogane and cupreous chafers is assumed to be an extremely effective means to solve the above problem.
The following methods are known as methods of synthesizing the pheromone of the mamekogane, i.e., (R,Z)-5-tetradecene-4-olide (18).
1) A method in which, as indicated by reaction formula (I) below, (4R,5S,6S)-5,6-dihydroxytetradecane-4-olide (40) as an optically active intermediate is derived from arabinose, an intermediate (41) is then derived from the intermediate (40), and diols at the 5- and 6-positions of the intermediate (41) are eliminated to obtain a compound (18) [Y. Nishida, M. Konno, H. Hori, H. Ohrui, H. Meguro, Agric. Biol. Chem., 51, 635 (1987)]: ##STR1## (wherein R.sub.1 represents C.sub.8 H.sub.17).
2) A method in which, as indicated by reaction formula (II) below, an acetylenic ketoester (52) synthesized from a 1-decyne derivative (51) is asymmetrically reduced (53) in the presence of (2S,3R)-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-but anol [Chirald available from Aldrich Chemical Co., Inc.] and LiAlH.sub.4, and the reduction product is subjected to fractional crystallization as an (R)-(+)-.alpha.-naphthylethylamine salt, thereby obtaining a compound (18) having high optical purity [S. Senda and K. Mori, Agric. Biol. Chem., 47, 2595 (1983)]. ##STR2## (wherein R.sub.1 represents C.sub.8 H.sub.17)
3) A method in which, as indicated by reaction formula (III), a compound (18) is obtained from (R)-glutamic acid, through butyrolactone, by using a Wittig reaction [R. E. Doolitle, et al, J. Chem. Ecol., 6,473 (1980)]. ##STR3## (wherein R.sub.1 represents C.sub.8 H.sub.17)
The conventional methods of manufacturing the compound (18) described above pose the following problems. Thus, in the method (1), a total of 12 steps are required from arabinose as the starting material, and the yield of the final compound (18) against arabinose is very low.
In the method (2), (2S,3R)-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-butanol and (R)-(+) -.alpha.-naphthylethylamine which are required to obtain the optically active compound (18) are very expensive reagents, resulting in high manufacturing costs. In addition, in order to finally obtain the compound (18) having high optical purity, the (R)-(+) -.alpha.-naphthylethylamine salt must be subjected to fractional crystallization, thus complicating the process.
In the method (3), when nitric acid is reacted with (R)-glutamic acid to close the lactone ring, tetrahydro-5-oxy-2-furanonecarboxylic acid which is partially racemized is obtained. The racemic product must be purified to (R)-(-)-tetrahydro-5-oxy-2-furanonecarboxylic acid having high optical purity. In the final step, a cumbersome Wittig reaction for purification must be performed. For this reason, purification is cumbersome and the process is complicated.
For descriptive convenience, the method of synthesizing (R,Z)-5-tetradecene-4-olide (18) as the pheromone of the mamekogane is exemplified. The same problems as described above are also posed by a method of synthesizing (R,Z)-5-dodecene-4-olide (28) as the pheromone of the cupreous chafer represented by formula (28). ##STR4## (wherein R.sub.2 represents C.sub.6 H.sub.13)
The present invention has been made in consideration of the above problems, and has as its object to provide a method of manufacturing a 4-substituted-.gamma.-lactone and a novel substance as an intermediate product thereof, which includes neither an optical purity step nor a practically difficult step, and can manufacture the target compound by a short process, and is suitable for mass production.